US4128510A - Vulcanizing halogen-containing polymers - Google Patents

Vulcanizing halogen-containing polymers Download PDF

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US4128510A
US4128510A US05/788,395 US78839577A US4128510A US 4128510 A US4128510 A US 4128510A US 78839577 A US78839577 A US 78839577A US 4128510 A US4128510 A US 4128510A
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carbon atoms
groups containing
thiadiazole
derivative
halogen
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John R. Richwine
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Hercules LLC
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Hercules LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring

Definitions

  • This invention relates to the crosslinking of halogen-containing polymers. More particularly this invention relates to a process of crosslinking halogen-containing polymers with certain derivatives of 2,5-dimercapto-1,3,4-thiadiazole and a basic material.
  • the mono- and dicarboxylic acid esters of 2,5-dimercapto-1,3,4-thiadiazole are known compounds and have been reported in the literature as light stabilizers (See U.S. Pat. No. 2,736,729) and lubricant additives (See U.S. Pat. No. 2,760,933), but not crosslinking agents.
  • the use of 2,5-dimercapto-1,3,4-thiadiazole as a curing agent for certain unsaturated polymers has been reported in British Pat. No. 974,915.
  • 2,5-dimercapto-1,3,4-thiadiazole tends to crosslink halogen-containing polymers prematurely (i.e.
  • saturated and unsaturated halogen-containing polymers can be readily crosslinked without sticking or premature curing (i.e. scorching) when certain derivatives of 2,5-dimercapto-1,3,4-thiadiazole are used in the presence of certain basic materials in normal vulcanization procedures.
  • this invention relates to a process of crosslinking saturated and unsaturated halogen-containing polymers with a derivative of 2,5-dimercapto-1,3,4-thiadiazole represented by one of the following formulas: ##STR1## wherein X is hydrogen, --CRR'OH, --(CH 2 --CH 1 --O) n H, ##STR2## where m is 2 to 10; n is 1 to 5; R and R' are hydrogen, alkyl groups containing 1-8 carbon atoms, or aryl, alkaryl or aralkyl groups containing 6 8 carbon atoms; R 2 is an alkyl group containing 1-17 carbon atoms, an aryl group with one or two rings, an alkaryl group containing 7-14 carbon atoms, an aralkyl group containing 7-8 carbon atoms or a cyclohexyl group; and R 3 is an alkyl group containing 1-8 carbon atoms; X' can be the same as X with the exception of hydrogen
  • Typical of the derivatives of 2,5-dimercapto-1,3,4-thiadiazole which can be used in the process of this invention are 5-mercapto-2-S-methylol-1,3,4-thiadiazole, 5-mercapto-1,3,4-thiadiazolyl-2-thiomethyl hemiacetal, 5-mercapto-1,3,4-thiadiazolyl-2-thiooctyl hemiacetal, 5-mercapto-1,3,4-thiadiazolyl-2-thiophenyl hemiacetal, 5-mercapto-1,3,4-thiadiazolyl-2-thiophenethyl hemiacetal, 5-mercapto-1,3,4-thiadiazolyl-2-thio-o,m, or p-ethylphenyl hemiacetal, 2-hydroxy-2-thio(5-mercapto)-S-methylol-1,3,4-thiadiazole, 5-mercapto-1,3,4-thiadiazolyl-2-thiomethyl
  • the monobenzoate and dibenzoate derivatives are particularly advantageous because they are easily prepared, easily handled, non-irritating, non-odorous, and particularly effective in the cross-linking.
  • Any saturated or unsaturated halogen-containing polymer i.e. containing at least about 1% most preferably about 5% by weight of halogen, may be crosslinked in accordance with the process of this invention.
  • Typical of the halogen-containing polymers are homopolymers of epichlorohydrin, copolymers of epichlorohydrin and ethylene oxide or propylene oxide, polychloroprene, chlorosulfonated polyethylnen, chlorinated high denisty polyethylene, polychloroalkylacrylates, poly(vinyl fluoride), poly(vinyl chloride), poly (vinylidene chloride), chlorobutyl rubber and bromobutyl rubber.
  • process of this invention may be used to crosslink blends of haolgen-containing polymers or haolgen-containing polymers blended with nonhalogen-containing polymers.
  • the only requirement is that there be sufficient halogen-containing polymer present in the blend to effect crosslinking.
  • halogen-containing polymers contain a small amount (i.e., from about 0.1% to about 2% by weight) of antioxidant, added at the time of their preparation. It may in some cases be desirable to add a small additional amount of antioxidant before or at the time of crosslinking the polymer.
  • antioxidants are phenyl- ⁇ -naphthylamine, di- ⁇ -naphthyl-p-phenylene-diamine, sym-di- ⁇ -napthyl-p-phenylenediamine, N-isooctyl-p-amino-phenol, the reaction product of diphenylamine and acetone, polymerized trimethyldihydroquinoline, 4,4'-thio-bis(6-tert.-butyl-m-cresol), the reaction product of crotonaldehyde and 3-methyl-6-tert.-butyl-phenol, nickel dibutyldithiocarbamate, the zinc salt of 2-mercapto-benzimidazole, and nickel dimethyldithiocarbamate.
  • a basic material or a material which will become basic on heating to the crosslinking temperature is required for use in conjunction with the derivative of 2,5-dimercapto-1,3,4-thiadiazole in the crosslinking process of this invention.
  • Typical inorganic materials are basic metal oxides and hydroxides and their salts with weak acids, such as, for example, lead oxides, zinc oxide, magnesium oxide, calcium oxide, calcium hydroxide, barium oxide, zinc carbonate, lead acetate, barium carbonate, sodium phenoxide and sodium acetate.
  • zinc oxide or zinc salts as the basic material in certain cases such as with chlorosulfonated polyethylene, chlorinated polyethylene, poly(vinyl chloride) or poly(vinylidene chloride), because zinc chloride formed in situ during the vulcanization process may cause undesirable degradtion by breaking of the polymer chain
  • an accelerator of the well-known types containing aliphatic or aromatic amine or quaternary nitrogen groups is the reaction product of buytraldehyde and aniline.
  • the polymers with which it is desirable to use an accelerator include poly(vinyl chloride), chlorinated polyethylene, homopolymer of epichlorohydrin, poly(vinyl fluoride) and poly(vinylidene chloride).
  • Varied amounts of the crosslinking agents can be added and the optimum amount of each crosslinking agent will depend upon the degree of crosslinking desired and the nature of the specific cross-linking agents employed. Generally, the amounts added (based on the weight of the polymer) will be within the following ranges: derivative of 2,5-dimercapto-1,3,4-thiadiazole, from about 0.1% to about 20%, preferably from about 0.5% to about 5.0%; basic material broadly from about 0.25% to about 50%, more preferably from about 0.5% to about 50%, most preferably from about 1.0% to about 20%; and accelerator (if one is used), broadly from about 0.01% to about 5%, more preferably from about 0.05% to about 5%, most preferably from about 0.1% to about 2%.
  • the crosslinking agents can be incorporated or admixed with the polymer in any desired fashion.
  • they can be uniformly blended with a polymer by simply milling on a conventional rubber mill or mixing in a Banbury mixer.
  • the agents are uniformly distributed throughout the polymer and uniform crosslinking is effected when the blend is subjected to heat. It is generally preferably to mill at temperatures within the range of from about 70° F. to about 200° F.
  • the blends unless compounded with a large amount of accelerator, are highly scorch-resistant below about 250° F.
  • Other methods of admixing the crosslinking agents with the polymer will be apparent to those skilled in the art.
  • crosslinking can be effected in minutes at elevated temperature or in days at temperatures slightly above room temperature (and in the presence of an accelerator).
  • the crosslinking temperature will be within the range of broadly from about 30° C. to about 280° C., more preferably from about 135° C. to about 235° C., and most preferably from about 150° C. to about 205° C.
  • the time will vary inversely with the temperature and will range from about 30 seconds to 70 hours, preferably from 30 seconds to about 120 minutes.
  • the crosslinking process can be conducted in the air at normal atmospheric pressure, it will generally be conducted in a metal mold under a compression of at least about 500 p.s.i. or in a steam autoclave at the pressure required for the desired temperature.
  • crosslinking agents In addition to the crosslinking agents, other ingredients can also be incorporated.
  • the additives commonly used in rubber vulcanization can be used here also, as, for example, extenders, fillers, pigments, plasticizers, softenera, etc.
  • extenders for example, extenders, fillers, pigments, plasticizers, softenera, etc.
  • carbon black is beneficial and, as in rubber compounding, gives very advantageous results. Obviously, there are many cases in which a filler is not required or desired and excellent results are achieved when only the crosslinking agents are added.
  • binders or carriers are polymers which may or may not be crosslinkable by the crosslinking agent.
  • Suitable materials are, for example, ethylene-propylene rubber, ethylene-propylene terpolymers, butadiene-styrene rubber, natural rubber, low density polyethylene, amorphous polypropylene and polyisobutylene.
  • Concentrations of the dimercaptothiadiazole derivative can vary from 20% to 90%, preferably from about 30% to 75%.
  • Other materials which cn advantageously be incorporated in the concentrates are accelerators, scorch retarders, antioxidants and non-basic fillers. The basic material should not be incorporated in the concentrate lest it decompose the thiadiazole derivative.
  • These polymer concentrates are normally stored and used in the form of sheets, extruded pellets or rods.
  • binders or carriers for use in the preparation of such easily handled concentrates are waxes, resins, or other low-melting solids.
  • Typical useful materials are paraffin wax, stearic acid, microcyrstalline wax, rosin, rosin esters and hydrocarbon resins.
  • This invention includes (1) the process of crosslinking halogen-containing polymers with the above described derivatives of 2,5-dimercapto-1,3,4-thiadiazole and at least one basic material; (2) the crosslinkable compositions comprising the halogen-containing polymers, derivatives of 2,5-dimercapto-1,3,4-thiadiazole and basic material; (3) the crosslinked composition resulting from the process of this invention; and (4) concentrates or dispersions of the cross-linkers in inert or crosslinkable polymers which are suitable for compounding into halogen-containing polymers which are to be cross-linked.
  • This example illustrates the preparation of the monobenzoate derivative of 2,5-dimercapto-1,3,4-thiadiazole.
  • This example illustrates the preparation of concentrates of the monobenzoate derivatives described in Example 1 in stearic acid or wax.
  • Each concentrate is prepared by dry blending the ingredients tabulated below, warming the concentrate blend to the melting point of the wax or stearic acid, extruding the melted concentrate blend and cutting the extrudate into rods or pellets.
  • This example illustrates the preparation of the dibenzoate derivative of 2,5-dimercapto-1,3,4-thiadiazole.
  • This example illustrates the preparation of the monoacetate derivative of 2,5-dimercapto-1,3,4-thiadiazole.
  • This example illustrates the preparation of the monocinnamate ester derovatove pf 2,5-dimercapto-1,3,4-thiadiazole.
  • the zinc salt derivative was prepared in a similar fashion from 10 parts of 2,5-dimercapto-1,3,4-thiadiazole and 9 parts of zinc chloride.
  • the zinc salt derivative was white.
  • the product analyzed 15.4% nitrogen and 52.8% sulfur compard with theoretical values for C 2 HN 2 S 3 -- Zn -- C 2 HN 2 S 3 of 12.9% nitrogen and 51.8% sulfur.
  • This example illustrates the use of the monobenzoate derivative of 2,5-dimercapto-1,3,4-thiadiazole, from Example 1, to crosslink an epichlorohydrin copolymer.
  • a masterbatch formulation of an equimolar copolymer of ethylene oxide and epichlorohydrin containing 24-26% chlorine, by weight and having a Mooney viscosity of 55, metal salt, carbon black, processing aid, antioxidants and plasticizers was compounded in a Banbury mixer.
  • the masterbatch formulation had the following composition:
  • Two portions of the above masterbatch formulation were compounded on a two-roll mill with crosslinking agents.
  • the first portion was compounded with the monobenzoate derivative prepared in Example 1.
  • the second portion was compounded with 2,5-dimercapto-1,3,4-thiadiazole (as a comparator).
  • the first portion processed satisfactorily on the two-roll mill.
  • the second portion i.e. comparator
  • This example illustrates the use of a predispersion of the monobenzoate derivative of Example 1 in crosslinking an epichlorohydrin copolymer.
  • a predispersion concentrate of the monobenzoate derivative having the following composition was prepared:
  • Example 9 To 100 parts of the masterbatch described in Example 9 was added 1.14 parts of the predispersion concentrate and the blend compounded on a two-roll mill. The blend exhibited excellent processing properties.
  • the resulting formulation was crosslinked by heating for 20 minutes at 160° C. in a steam autoclave.
  • the crosslinked product had a tensile strength of 1340 p.s.i., % elongation of 300, 100% modulus of 610 p.s.i. and a Shore A hardness of 69.
  • Mooney scorch resistance (measured at 121° C.) was 16.0 minutes for a 3 point rise in viscosity and 23 minutes for a 5 point rise in viscosity.
  • This example illustates the crosslinking of polychloroprene in accordance with the process of this invention.
  • a portion of a masterbatch formulation was compounded on a two-roll mill with the crosslinking agents and then crosslinked by heating at 153° C. for thirty minutes in a oscillating disc rheometer (American Standard testing method D 2705-68T.
  • the parts of cross-linker used and the physical properties are tabulated below.
  • This example illustrates the use of an accelerator in the crosslinking process of this invention.
  • a masterbatch formulation of the equimolar copolymer of ethylene oxide and epichlorohydrin described in Example 9, carbon black, metal salt, antistatic agent, and antioxidant was compounded in a Banbury mixer.
  • the masterbatch formulation had the following composition.
  • This example illustrates the crosslinking of a bromine containing polymer in accordance with the process of this invention.
  • a masterbatch formulation of brominated poly(isobutyleneisoprene) elastomer, "Bromobutyl” containing 1.5% bromine by weight (sold by Polymer Corporation Ltd.), carbon black, processing aid, and metal oxides was compounded in a Banbury mixer.
  • the masterbatch formulation had the following composition:
  • This example illustrates the crosslinking of chlorinated polyethylene in accordance with the process of this invention.
  • a masterbatch formulation of chlorinated polyethylene containing 36% chlorine by weight (sold by Dow Chemical Company), carbon black, stabilizer, plasticizer and antioxidant was compounded in a Banbury mixer.
  • the masterbatch formulation had the following composition:
  • a masterbatch formulation of the copolymer of ethylene oxide and epichlorohydrin described in Example 9, carbon black, processing aid, antioxidant, accelerator, and basic material was compounded in a Banbury mixer.
  • the masterbatch formulation had the following composition:
  • a masterbatch formulation of the copolymer of ethylene oxide and epichlorohydrin described in Example 9, carbon black, processing acid, and antioxidants was compounded in a Banbury mixer.
  • the masterbatch formulation had the following composition:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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US4288576A (en) * 1978-09-15 1981-09-08 Hercules Incorporated 2,5-Dimercapto-1,3,4-thiadiazole as a cross-linker for saturated, halogen-containing polymers
US4306988A (en) * 1980-11-10 1981-12-22 Olin Corporation Selected poly(oxyalkylated) 1,3,4-thiadiazoles and their use as corrosion inhibitors
US4329475A (en) * 1980-11-10 1982-05-11 Olin Corporation Selected poly(oxyalkylated) 1,3,4-thiadiazoles and their use as corrosion inhibitors
US4349458A (en) * 1980-11-10 1982-09-14 Olin Corporation Selected poly(oxyalkylated) 1,3,4-thiadiazoles in acid baths and their use as corrosion inhibitors
US4399262A (en) * 1982-04-12 1983-08-16 The B. F. Goodrich Company Acrylate rubber compositions
US4482681A (en) * 1981-10-22 1984-11-13 Hercules Incorporated Crosslinking halogen-containing polymers
US4551505A (en) * 1983-10-08 1985-11-05 Rhein-Chemie Rheinau Gmbh Process for crosslinking chlorinated polyethylene
US4594396A (en) * 1984-12-05 1986-06-10 Hercules Incorporated Cross-linking halogenated polymers
US4734457A (en) * 1987-05-07 1988-03-29 R. T. Vanderbilt Company, Inc. Rubber compositions containing polymeric phenol derivatives of 1,3,4-thiadiazole
US4753971A (en) * 1987-07-10 1988-06-28 The Dow Chemical Company Chlorinated polyethylene elastomer composition having enhanced resistance to ozone-induced cracking
US4806393A (en) * 1986-03-30 1989-02-21 Yeda Research And Development Company Limited Prevention of plasticizer migration from PVC products
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US4910245A (en) * 1988-04-07 1990-03-20 The Dow Chemical Company Thermoplastic elastomers based upon chlorinated polyethylene and a crystalline olefin polymer
US4920165A (en) * 1987-07-07 1990-04-24 Mobay Corporation Scorch retarder for halogenated elastomers
US4978703A (en) * 1990-01-04 1990-12-18 The Dow Chemical Company Thermoplastic elastomers based upon chlorinated polyethylene and a crystalline olefin polymer
US4978716A (en) * 1988-04-07 1990-12-18 The Dow Chemical Company Thermoplastic elastomers based upon chlorinated polyethylene and a crystalline olefin polymer
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US5665830A (en) * 1993-12-16 1997-09-09 Hercules Incorporated Controlling premature curing of vulcanizable halogen-containing polymers
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US20060205889A1 (en) * 2005-03-14 2006-09-14 Dow Global Technologies Inc. Vulcanizable chlorinated elastomer compositions with improved processing safety and cure rate
US20090326143A1 (en) * 2006-08-30 2009-12-31 Laakso Jr Raymond L Cure system for halogenated elastomer compositions, a curable halogenated elastomer composition, and a method for curing halogenated elastomer compositions
US20100010152A1 (en) * 2006-08-30 2010-01-14 Laakso Jr Raymond L Cure system of halogenated elastomer compositions, a curable halogenated elastomer composition, and a method for curing halogenated elastomer compositions
EP2330150A1 (en) 2009-12-07 2011-06-08 The Goodyear Tire & Rubber Company Rubber composition containing silica reinforcement and method of preparing such a rubber composition
FR2975996A1 (fr) * 2011-06-06 2012-12-07 Mlpc Internat Composition de vulcanisation pour polymeres insatures
CN103597023A (zh) * 2011-04-14 2014-02-19 米其林企业总公司 包含噻二唑衍生物的橡胶组合物
CN104387339A (zh) * 2014-11-18 2015-03-04 天津理工大学 一种含有脂肪链的噻二唑衍生物及其制备方法
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CA1124445A (en) * 1977-10-17 1982-05-25 Hercules Incorporated 2,5-dimercapto-1,3,4-thiadiazole as a cross-linker for saturated, halogen containing polymers
JPS61238838A (ja) * 1985-04-17 1986-10-24 Kagakuhin Kensa Kyokai ゴム加硫剤
DE3535137A1 (de) * 1985-10-02 1987-04-02 Bayer Ag Kautschukmischung und daraus hergestellte covulkanisate
DE4013714A1 (de) * 1990-04-28 1991-10-31 Rhein Chemie Rheinau Gmbh Verfahren zum vernetzen von halogenhaltigen polymeren
JP3496736B2 (ja) * 1994-08-25 2004-02-16 株式会社トクヤマ 接着用表面処理剤
WO2014119517A1 (ja) * 2013-01-30 2014-08-07 電気化学工業株式会社 クロロプレンゴム組成物及び加硫成形体
JP2014169378A (ja) * 2013-03-04 2014-09-18 Denki Kagaku Kogyo Kk ゴム組成物及び加硫発泡成形体
WO2023090931A1 (ko) 2021-11-18 2023-05-25 주식회사 엘지화학 폴리에틸렌 및 이를 이용한 가황성 염소화 폴리에틸렌 조성물

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NL190667B (nl) 1994-01-17
FR2356687B1 (enrdf_load_stackoverflow) 1983-12-02
CH622273A5 (enrdf_load_stackoverflow) 1981-03-31
SE7707402L (sv) 1977-12-29
CA1112789A (en) 1981-11-17
ATA452677A (de) 1982-02-15
BE856222A (fr) 1977-12-28
DK286677A (da) 1977-12-29
DE2728772C2 (de) 1986-04-03
GB1536593A (en) 1978-12-20
NL7707131A (nl) 1977-12-30
ES460115A1 (es) 1978-05-01
NL190667C (nl) 1994-06-16
AT368541B (de) 1982-10-25
IT1080768B (it) 1985-05-16
DK159657B (da) 1990-11-12
DK159657C (da) 1991-04-08
JPS5921344B2 (ja) 1984-05-19
SE432432B (sv) 1984-04-02
DE2728772A1 (de) 1977-12-29
JPS533439A (en) 1978-01-13
FR2356687A1 (fr) 1978-01-27

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